Sealing of glass to metal



' l atented May 7,

UNITED STATE s' PATENT OFFICE SEALING OF GLASS TO METAL Raymond L. Taylor, New Providence, N. 1., as-

signor to Bell Telephonel aboratories, Incorporated, New York, N. Y

a corporation of New York No Drawing. Application July 28, 1943, Serial No. 496,523 g 11 Claims. (on. 49-81) This invention relates to a process for forming a sealbetween metal and glass, and more particularly to such a process employing a flux which makes possible the ready formation of a seal bea tween glass and a metal which otherwise resists the formation of a seal between the metal and glass.

While methods have been known for forming seals between glassand various types of metals, it has heretofore been founddifiicult, if not impossible, to form satisfactory seals between glass and tantalum metal or zirconium metal. Yet it is highly desirable that it be, possible to form between glass and such metalsstrong seals which are gas-proof and/or liquid-proof for various continue of its own accord, the reaction being strongly exothermic. Consequently, before a temperature is reached which is high enough to cause the oxide to dissolve in the glass to form 'a seal between the metal and glass, the thickness of the oxide film becomes excessive and uncontrollable. This excessively thick oxide film, as was indicated above, causes poor adherence between the glass and the metal and permits leaktypes of apparatus such as-electron discharge devices, electrolytic condensers, etc.

- It has been established that to form a satisfactory strong seal between a metal and glass,

the glass and will also permit leakage of liquids or. gases along the interface between the oxide and the metal.

Tantalum metal and zirconium metal each has an oxide film on its surface which is developed upon exposure of the metal to the atmosphere and which serves to passivate the surface of the metal or render it resistant to corrosion. In the development of the present invention, however, it was found that certain common properties of these metals and of their oxide films rendered it extremely difiicult'under ordinary conditions to form a satisfactory seal between such a metal and glassl I each of these metals is of such a nature that a high temperature is required to cause the oxide It appears that the oxide film on of the film to dissolve in glass. But at such ele" vated temperatures eachof these metals-chemically combines with substantial quantities of oxygen from the air.v Therefore, as the metal is heated in th presence of oxygen to, a tempera- .ture sufiicient to cause the. oxide of. the film to dissolve in glass a temperature is reached at which oxidation begins suddenly, and unless the temperature is sharply reduced, will vigorously age of gases or liquids through the seal.

Moreover, it is characteristic of each of these metals, and particularly of zirconium, that its oxide diffuses into the metal as the metal is heated; such diffusion of the oxide embrittles and otherwise adversely affects the metal.

The above difiiculties are largely, if not entirely, overcome and a seal which is strong, proof against leakage of gases or liquids, endotherwise satisfactory, may be readily formed between tantalum or zirconium metal and glass-by the process of the invention, according to which a fiux is employed which comprises'at least one fluoride of an alkali metal or alkaline earth metal.

e. g., lithium, sodium, potassium, rubidium. cesium, beryllium, magnesium, calcium, stron-' tium and barium. According to the present invention, glass of suitable characteristics in the molten state is applied to the surface of the tantalum or zirconium metal in the presence of such a fiux, and is then solidified.-

The flux. apparently operates to promote the solution of the oxideof the metal in the glass and thus permits the formation of a seal at a temperature lower than that which would otherwise be operative. Since a lower temperature is employed, excessive oxidation of the metal due to the gettering action of the metal, and embrittlement of the metal due to diffusion of the oxide during heating of the metal are minimized if not wholly avoided. Furthermore, the presence of the flux on the surface of the metal is surprisingly effective in inhibiting oxidation of the surface when the metal is heated; this also pre- 'vents excessive oxidation and deleterious em- .brittiement of the metal. The flux also acts to promote parently alkaline wetting of the metal by the glass, ap-

wetting makes possible good contact between the glass and metal and retards deleterious oxidation of the metal. These fluorides are also readily absorbed by the glass and hence do not harm the seal between the glass and metal. For the above reasons the flux makes possible the production without. difllculty.

because the alkali metal fluorides and earth metalfiuorides attack both the glass and the metal; such of seals between glass and zirconium and tantalum metals which are strong and leak-proof.

The glass employed should, of course, have a temperature coemcient of expansion and other which has on its surface the fluoride flux is contacted with the molten glass. For best results, the temperature of the glass should be as low as is possible to obtain without loss of wetting ping or otherwise applying to the surface of the metal to be sealed to the glass a solution containing the flux if it is one which is substantially soluble such as sodium fluoride; advantageously the solution is a saturated solution, al- 60 though lesser concentrations may be employed. Alternatively, a suspension of the finely divided flux in a suitable evaporable liquid may be applied to the metal. If a solution or suspension is employed, it is advantageous to evaporate the liquid to deposit the flux on the metal before sealing the metal to the glass. As another example, the wire or other article of.the metal may be contacted with the fluoride salt in solid form; thus, the wire, preferably while heated, may be inserted into a mass of finely divided salt so that some of the salt adheres to the surface of the wire.

In the sealing operation the metal article such characteristics which are suitable to permit the 5 characteristics; this prevents excessive oxidation formation of a strong seal between the glass and of the surface of the metal which causes the metal. The temperature coefiicient of expansion v above-indicated disadvantageous results, while of the glass should be approximately the same as the presence of the flux promotes the desired that of the metal to which the glass is to adhere; dissolving of the oxide on the metal in the glass this is necessary to prevent the development in l at such low temperature to permit the formation the glass of stresses which would cause the glass of a satisfactory seal. After the seal is formed to fracture upon temperature changes as occur between the molten glass and the metal, the upon cooling or in operation of the apparatus glass is cooled until it solidifies. Thereafter, the containing the glass-to-metal seal. Examples of glass may be annealed, if desired, to relieve glasses, and their compositions by weight, which stresses. The physical techniques of forming the have been successfully employed in the formation seals are known to those skilled in the art and of seals between tantalum metal and glass and require no. further discussion. between zirconium metal and glass are The present invention thus provides a process Miscel- Nzlmc of glass SiO: NiliO-KIO B301 PbO A1103 lanenus oxides Corning thermometer glass 752 72 i0 10 5 3 Corning Nonex" 772 73 4. 5 16.6 o Corning "Pyrex 774 80.5 4.2 12.9 2.2 fl 2 Other glasses having suitable expansion and other which is simple, inexpensive, highly effective, and characteristics may, of course, be employed. which overcomes the prior difficulties heretofore The metal which may be sealed according to. encountered in forming satisfactory seals bethe present invention may be tantalum or zirtween glass and tantalum or zirconium metal. conium metal as such, or an alloy containing a The process of the present invention makes pospredominant proportion of either of said metals sible the formation of seals which are strong and and having the characteristics of said metal and which do not permit leakage of gases or liquids, which is, therefore, difficult to seal to glass. without excessive oxidation or embrittiement of While metal articles of various shapes and sizes the metal. may be sealed to glass according to the present The process of the present invention finds wide invention, the invention is particularly applicable application in various arts; for example, it is to the sealing of wires of metal since these are extremely useful in the manufacture of electromost used. It is advantageous that the surface lytic condensers employing filmed tantalum or of the metal which is to be sealed to the glass zirconium electrodes, which electrodes are conbe clean. This may be accomplished by washing nected to tantalum or zirconium lead wires passthe metal in suitable solvents, chemical cleaners, ing through the walls of glass containers for the or the like. electrolyte. It is also useful in sealing tantalum The flux may consist of any one or more of the or zirconium to glass in the manufacture of elecabove-indicated fluorides; however, sodium fluo- 5 tron discharge devices, incandescent light bulbs, ride appears to be the most advantageous because etc. of its ready availability, its substantial solubility Various modifications may be made in the which permits easy application, and the ease above-described processes embodying the present with which it may be employed. invention, and the process of the present inven- The flux may be employed in various manners; tion may be employed for various uses other than the primary deslderatum is to have the flux in those indicated. contact with the surface of the metal to be It is intended that the patent shall cover by sealed to the glass while the molten glass is suitable expression in the appended claims whatbeing applied thereto. ever features of patentable novelty reside in the The flux, for example, may be applied by dipinvention.

What is claimed is:

1. The process of forming a seal between glass and a body of a metal chosen from the group consisting of tantalum and zirconium comprising applying molten glass to a surface of said metal body while said surface is in contact with a fiux comprising essentially at least one fluoride of a metal chosen from the group consisting of the metal chosen from the group consisting of alkali alkali metals and the alkaline earth metals.

2. The process of forming a seal between glass and a body of a metal chosen from the group consisting of tantalum and zirconium comprising depositing on a surface of said metal body a flux comprising essentially at least one fluoride 01' a metals and alkaline earth metals, and thereafter applying a molten glass to said surface,

3. The process of forming a seal between glass and a body of tantalum metal comprising applyas wire which is to be sealed to the glass and ing molten glass to a surface of said metal body while said surface is in contact with a flux comprising essentially at least one fluoride of a metal chosen from the group consisting of the alkali metals and the alkaline earth metals.

4. The process of forming a seal between glass and. a body of zirconium metal comprising applying molten glass to a surface of said metal body while said surface is in contact with a nu: come prising essentially at least one fluoride of a metal chosen from the group consisting of the alkali metals and the alkaline earth metals.

5. Theprocess of forming a seal between glass and a body of a metal chosen from the group consisting of tantalum and zirconium comprising depositing on a surface of said metal body a solution in which the solute comprises essentially at least one fluoride of a metal Iran the group consisting of the alkali metals and the alkaline earth metals, and thereafter will!!! a molten glass tosaid surface. I

6. The process of forming aseal between glass and a body of tantalum metal comprising degroup consisting oithe alkali metals and the alkaline earth metals, and' thereafter applying -a molten glass to said surface. v

8. The process of forming a seal between glass and a body of a metal chosen from the group consisting' of tantalum and zirconium comprising depositing on a surface of said metal body a dry flux comprising essentially at least one fluoride ofa metal chosen from-the group consisting of the alkali metals and the alkaline earth metals, and thereafter applying a molten glass to said surface.

9. The process of forming a seal between glass and a body of tantalum, metal comprising depositing on a surface of said metal body a solution in which the solute comprises, essentially at least one fluoride of a metal chosen from theand thereafter applying a molten glass to said group consisting of the alkali metals and the al-. kalineearth metals. and thereafter applying a molten glass to said surface.

'7. The process of forming a seal between glass and a body of zirconium metal comprising depositing on a surface of said metal body a solu tion in which the solute'comprise's essentially a least one fluoride of a metal chosen from the positing on a surface positing on a surface of said metal body a dry flux comprising essentially at least one fluoride of a metal chosen from the group consisting of the alkali metals and the alkaline earth metals, and

thereafter plying a molten glass to said surface.

10. The process of forming a seal between glass and a body of zirconium metal comprising deof said metal body a dry flux comprising essentially at least one fluoride of a metal chosen from the'group consisting of the alkali metalsand the alkaline earth metals,

surface.

11. The process and a body of a metal chosen from the group consisting of tantalum and zirconium comprising applying molten glass to a surface of said body while said surface is in contact with a flux comprising essentially sodium fluoride. RAYMOND L. TAYLOR.

of forming a seal between glass 

